Alkylphosphonate diesters and monoesters of N-phosphonomethylglycinate as herbicides

ABSTRACT

Alkylphosphonate diesters and monoesters of N-phosphonomethylglycine are disclosed which are useful as herbicides. This invention further relates to herbicidal compositions containing such alkylphosphonate diesters and monoesters of N-phosphonomethylglycine and to herbicidal methods employing such compounds and compositions.

This is a continuation in part of U.S. application Ser. No. 275,461,filed June 19, 1981 now abandoned.

This invention relates to mono and diesters ofN-phosphonomethylglycinate which are useful as herbicides. Moreparticularly this invention relates to alkyl phosphonate mono anddiesters of N-phosphonomethylglycinate which are useful as herbicidesand to herbicidal methods employing such compounds and compositions.

U.S. Pat. No. 4,025,331 issued to Jean-Pierre Leber on May 24, 1977discloses N-phosphonomethylglycine derivatives of the formula ##STR1##wherein X is hydrogen, unsubstituted or substituted hydrocarbon or acation and M is hydrogen or a cation. The compounds disclosed in U.S.Pat. No. 4,025,331 supra are said to possess herbicidal and plant growthregulating properties.

The compounds of the present invention are represented by the formula##STR2## wherein R is lower alkyl; R₁ is a ##STR3## group wherein n isan integer of from 0 to 4, L is hydrogen or lower alkyl and Y isselected from the group consisting of trihalomethyl, alkoxycarbonyl,furanyl, pyrrolidinyl, pyranyl group and a ##STR4## group wherein Z andZ₁ are independently lower alkyl, and R₂ is hydrogen or a grouprepresented by R₁.

As employed throughout the claims and description, the term "loweralkyl" includes alkyl radicals which have up to four carbon atoms in astraight or branched chain, for example, methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl and t-butyl.

In accordance with the present invention alkylphosphonate diesters ofN-phosphonomethylglycinate of the formula ##STR5## may be prepared bysimultaneously reacting a trialkylphosphite of the formula

    P(OR.sub.1).sub.3                                          ( 11)

wherein R₁ is defined as recited above with water and with1,3,5-tri-(alkoxycarbonylmethyl) hexahydro-1,3,5-triazine (trimer of theSchiff's base of formaldehyde and a corresponding lower alkyl glycinate)of the formula ##STR6## wherein R is as aforedefined to form a crudediester composition containing diester product. A purified diesterproduct may be recovered from the crude diester composition by employingdistillation means as, for example, employing a chromatographic ordistillation means having sufficient capability and capacity to effectthe aforedescribed recovery.

The triester component of the reaction mixture can be obtained byreacting phophorous trichloride with three equivalents of thecorresponding alcohol (R₁ OH) in the presence of a base such astriethylamine in a suitable solvent. Such a process is described in"Organic Phosphorous Compounds" (Vol. 5) by G. M. Kosolapoff and L.Maier (Wiley-Interscience, 1973) at pp. 32-37.

The triazine components used in the above-described process are wellknown condensation products of formaldehyde with an amine. Triazines ofthe type useful in the present invention are described for example, in"S-Triazines and Derivatives" by E. M. Smolin and L. Rapoport,(Interscience 1959), pp. 480-3.

The aforedescribed reaction is carried out at a temperature in the rangefrom about 10° to 110° and preferably from about 20° to about 100° C.

In preparing diester compounds of formula (1), the range of reactants isnot narrowly critical. Preferably, however for each mole oftrialkylphosphite employed, one should employ from about 0.5 to about1.5 mole water, about 1/4 to about 1/2 mole1,3,5-tri-l(alkoxycarbonylmethyl)hexahydro-1,3,5-triazine.

While no catalyst is required for the aforedescribed reaction to proceeda catalyst may be employed if desired.

The reaction time is in the range from about 1 to about 72 and ispreferably from about 2 to about 50 hours.

While the process of this invention can be conducted at atmospheric,sub-atmospheric or super-atmospheric pressure, for convenience andeconomy it is generally preferred to conduct these processes atatmospheric pressure.

Although a suitable solvent may be employed in the aforedescribedprocess, it is preferred that the reaction be carried out in the absenceof a solvent.

Suitable agitation is provided, preferably by stirring or otherwiseagitating the reaction composition.

In practicing the aforedescribed process the aforedescribed reactantsare admixed together in any desired order to form the reactioncomposition.

The following Examples are presented to define the invention morecompletely without any intention of being limited thereby. All parts andpercentages are by weight, unless otherwise specified.

As indicated above the triphosphite esters are obtained by the reactionof phosphorous trichloride with the appropriate alcohol in the presenceof a base. The triphosphite esters employed in the following Examplesare prepared using the following alcohols: ##STR7##

EXAMPLE 1

A reaction composition comprising 15.0 g (0.045 mole)tri-(2-furanylmethyl)phosphite, 0.81 g (0.045 mole) water, and 5.18 g(0.015 mole) 1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine washeated at about 100° to about 110° C. for a time of 3 hours. An alcohol,2-furanylmethanol coproduct was removed by employing bulb to bulbdistillation of the reaction mixture at 75° C. and 0.05 mm Hg. Thedistillation residue was chromatographed on silica gel with an eluent ofethyl acetate. The product, glycine,N-[[bis(2-furanylmethoxy)phosphinyl]methyl]-, ethyl ester was obtainedas a viscous yellow oil in 36.6% yield (6.0 g) having the followinganalysis:

Calc'd: C, 49.31; H, 7.72; N, 3.83; P, 8.48; Found: C, 49.45; H, 8.33;N, 3.38; P, 7.56.

EXAMPLE 2

A reaction composition comprising 15.0 g (0.0353 mole)tri-[(2,2-dimethyl-1,3-dioxolan-4-yl)methyl]phosphite, 0.64 g (0.0353mole) water, and 4.07 g (0.0118 mole)1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was heated atabout 100° to about 110° C. for a time of 4 hours. An alcohol2,2-dimethyl-1,3-dioxolan-4-yl methanol coproduct was removed byemploying bulb to bulb distillation of the reaction mixture at 80° C.and 0.1 mm Hg. The distillation residue was chromatographed on silicagel with an eluent of ethyl acetate. The product, glycine,N-[[(bis[(2,2-dimethyl-1,3-dioxolan-4-yl)methoxy]phosphinyl]methyl]-,ethyl ester was obtained as a viscous yellow oil in 35% yield (5.2 g)having the following analysis:

Calculated: C, 48.00; H, 7.58; N, 3.29; P, 7.28; Found: C, 48.57; H,7.60; N, 2.74; P, 6.73.

EXAMPLE 3

A reaction composition comprising 15.0 g (0.04 mole)tri-[(tetrahydro-2H-pyran-2-yl)methyl]phosphite, 0.72 g (0.04 mole)water, and 4.6 g (0.0133 mole)1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was heated atabout 100° to about 110° C. for a time of 3 hours. An alcohol(tetrahydro-2H-pyran-2-yl) methanol coproduct was removed by employingbulb to bulb distillation of the reaction mixture at 75° C. and 0.1 mmHg. The distillation residue was chromatographed on silica gel with aneluent of ethyl acetate. The product, glycine,N-[(bis(tetrahydro-2H-pyran-2-yl methoxy)phosphinyl]methyl]-, ethylester was obtained as a viscous yellow oil in 57% yield (9.0 g) havingthe following analysis:

Calculated: C, 51.90; H, 8.20; N, 3.56; P 7.87; Found: C, 51.86; H,8.34; N, 3.37; P, 7.48.

EXAMPLE 4

A reaction composition comprising 15.0 g (0.0402 mole)tri-[2-(1-pyrrolidinyl)ethyl]phosphite, 0.72 g (0.0402 mole) water, and4.63 g (0.0134 mole)1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was heated atabout 25° C. for 1 hour and then at about 100° to about 110° C. for 3hours. The reaction mixture was chromatographed on microcrystallinecellulose with an eluent of ethyl acetate. The product, glycine,N-[[(bis[2-(1-pyrrolidinyl)ethoxy]phosphinyl]methyl]-, ethyl ester wasobtained as a viscous yellow oil in 41.3% yield (6.5 g) having thefollowing analysis:

Calculated: C, 52.16; H, 8.75; N, 10.74; P, 7.91; Found: C, 52.62; H,8.42; N, 10.85; P, 6.43.

EXAMPLE 5

A reaction composition comprising 15.0 g (0.0353 mole) butanoic acid,(3,3',3"-phosphinidyne tris(oxy)tris-,triethyl ester, 0.64 g (0.0353mole) water, and 4.08 g (0.0118 mole)1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was heated atabout 100° to about 110° C. for a time of 3 hours. An alcohol coproductethyl 3-hydroxybutanoate was removed by employing bulb to bulbdistillation of the reaction mixture at ≦80° C. and 0.1 mm Hg. Thephosphonate monoester product was obtained from a solution of ethylacetate of the distillation residue upon standing at about 25° C. for 48hours. The product butanoic acid,3-[[[[(2-ethoxy-2-oxoethyl)amino]methyl]hydroxyphosphinyl]oxy]-, ethylester was obtained as a white solid in 8% yield (0.9 g) having a meltingpoint of 116°-118° C. and having the following analysis:

Calculated: C, 42.44; H, 7.12; N, 4.50; P, 9.95; Found: C, 42.05; H,7.11; N, 4.31; P, 9.98.

EXAMPLE 6

A reaction composition comprising 15.0 g (0.0315 mole)tri-(2,2,2-trichloroethyl)phosphite, 0.57 g (0.0315 mole) water, and3.63 g (0.0105 mole)1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was heated atabout 100° to about 110° C. for a time of 3 hours. The reaction mixturewas chromatographed on microcrystalline cellulose with an eluent ofethyl acetate. The product was precipitated from ethyl acetate eluentduring 12 hours standing at 25° C. The product, glycine,N-[[(2,2,2-trichloroethoxy)hydroxyphosphinyl]methyl]-, ethyl ester,hydrate was obtained as a white solid in 14.7% yield (1.6 g) having amelting point of 143°-145° C. and having the following analysis:

Calculated: C, 24.26; H, 4.36; N, 4.04; P, 8.94; Found: C, 24.42; H,3.48; N, 3.66; P, 7.87.

EXAMPLE 7

A reaction composition comprising 15.0 g (0.0315 mole)tri-(2,2,2-trichloroethyl)phosphite, 0.57 g (0.0315 mole) water, and3.63 g (0.0105 mole)1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was heated atabout 100° to about 110° C. for a time of 3 hours. The reaction mixturewas chromatographed on micro-crystalline cellulose with an eluent ofethyl acetate. Upon standing for 12 hours at about 25° C. a hydratedform of the product precipitated. Upon standing the ethyl acetatefiltrate after an additional 12 hours at 25° C. deposited the presentproduct which was collected and dried at 40° C. and 0.1 mmHg over P₂ O₅.The product, glycine,N-[[hydroxy(2,2,2-trichloroethoxy)phosphinyl]methyl]-, ethyl ester wasobtained as a white solid in 10.6% yield (1.1 g) having a melting pointof 197°-199° C. and having the following analysis:

Calculated: C, 25.59; H, 3.99; N, 4.26; P, 9.43; Found: C, 25.85; H,3.74; N, 4.44; P, 9.31.

If desired, a diester of formula (I) may be hydrolysized to a monoesterof formula (I) by controlled hydrolysis. The temperature is in the rangefrom about 15° to about 50° C. and is preferably from about 20° to about30° C. The hydrolysis time is in the range from abou 10 to about 60 andpreferably from about 20 to about 40 minutes.

EXAMPLE 8

This Example illustrates the production of a monosubstituted phosphonatefrom the corresponding disubstituted phosphonate derivative.

A reaction composition comprising 8.0 g (0.028 mole) of ethyl N[[bis1-(1-methoxycarbonyl)ethoxy]phosphinyl]methylglycinate illustrative of adiester compound of formula (I) and 0.51 g (0.028 mole) water wasagitated at about 25° C. for 30 minutes. The reaction mixture waschromatographed on a cation exchange column with water as eluent. Theproduct, propanoic acid,2-[[[[(2-ethoxy-2-oxoethyl)amino]methyl]hydroxyphosphinyl]oxy]-, methylester hydrate was isolated as the fourth component determined by arefractive index detector in 41.6% yield (3.30 g) having the followinganalysis and formula:

Calculated: C, 36.10; H, 6.67; N, 4.68; P, 10.34; Found: C, 36.18; H,6.11; N, 4.56; P, 10.38. ##STR8##

EXAMPLE 9

The post-emergent herbicidal activity of some of the various compoundsof this invention was demonstrated by greenhouse testing in thefollowing manner. A good grade of top soil is placed in aluminum panshaving holes in the bottom and compacted to a depth of 0.95 to 1.27 cm.from the top of the pan. A predetermined number of seeds of each ofseveral dicotyledonous and monocotyledonous annual plant species and/orvegetative propagules for the perennial plant species were placed on thesoil and pressed into the soil surface. The seeds and/or vegetativepropagules are covered with soil and leveled. The pans are then placedon a sand bench in the greenhouse and watered from below as needed.After the plants reach the desired age (two to three weeks), each panexcept for the control pans is removed individually to a sprayingchamber and sprayed by means of an atomizer operating at a positive airpressure of approximately 1.46 kg/cm² absolute. The atomizer contains 6ml of a solution or suspension of the chemical. In that 6 ml. is anamount of a cyclohexanone emulsifying agent mixture to give a spraysolution or suspension which contains about 0.4% by weight of theemulsifier. The spray solution or suspension contains a sufficientamount of the candidate chemical in order to give application ratescorresponding to those set forth in the tables. The spray solution isprepared by taking an aliquot of a 1.0% by weight stock solution orsuspension of the candidate chemical in an organic solvent such asacetone or tetrahydrofuran or in water. The emulsifying agent employedis a mixture comprising 35 weight percent butylamine dodecylbenzenesulfonate and 65 weight percent of a tall oil ethylene oxide condensatehaving about 11 moles of ethylene oxide per mole of tall oil. The pansare returned to the greenhouse and watered as before and the injury tothe plants as compared to the control is observed at approximately twoand four weeks as indicated in the tables under WAT and the resultsrecorded. In some instances, the two-week observations are omitted.

The post-emergent herbicidal activity index used in Tables I and II isas follows:

    ______________________________________                                        Plant Response  Index                                                         ______________________________________                                        0-24% control   0                                                             25-49% control  1                                                             50-74% control  2                                                             75-99% control  3                                                             100% control    4                                                             ______________________________________                                    

The plant species utilized in these tests are identified by letter inaccordance with the following legend:

    ______________________________________                                        A -- Canada Thistle*                                                                             K -- Barnyardgrass                                         B -- Cocklebur     L -- Soybean                                               C -- Velvetleaf    M -- Sugar Beet                                            D -- Morningglory  N -- Wheat                                                 E -- Lambsquarters O -- Rice                                                  F -- Smartweed     P -- Sorghum                                               G -- Yellow Nutsedge*                                                                            Q -- Wild Buckwheat                                        H -- Quackgrass*   R -- Hemp Sesbania                                         I -- Johnsongrass* S -- Panicum Spp                                           J -- Downy Brome   T -- Crabgrass                                             ______________________________________                                         *Established from vegetative propagules.                                 

                  TABLE I                                                         ______________________________________                                        Compound                                                                      of                                                                            Example            Plant Species                                              No.     WAT     kg/h   A   B   C   D   E   F   G HIJ K                        ______________________________________                                        1       4       56.0   3   2   1   2   2   1   11112                                  4       11.2   0   0   0   1   0   0   00000                          2       4       56.0   2   2   2   2   3   3   23123                                  4       11.2   0   0   0   1   0   0   00003                          3       4       11.2   0   0   0   1   0   1   00 -- 01                               2        5.6   0   0   0   0   0   0   00000                          4       4       11.2   1   2   1   2   1   2   12213                                  4        5.6   1   1   1   1   3   2   21102                          5       4       11.2   1   2   1   2   0   0   21202                                  4        5.6   0   0   0   1   0   0   00 101                         6       4       11.2   0   1   0   0   1   0   00001                                  4       56.0   0   1   0   1   1   1   00001                          7       4       11.2   2   2   2   2   3   2   21003                                  4        5.6   1   2   1   2   3   2   01203                           8**    4       11.2   1   2   2   3   3   3   32312                                  4        5.6   1   1   0   1   0   0   10212                          ______________________________________                                         **Sprayed in 100 gallon per acre tetrahydrofuran immediately after            formulation.                                                             

                                      TABLE II                                    __________________________________________________________________________    Compound of   Plant Species                                                   Example No.                                                                          WAT kg/h                                                                             L M N O P B Q D R E F C J S K T                                 __________________________________________________________________________    2      4   5.6                                                                              0 0 1 0 1 0 2 1 --                                                                              0 --                                                                              1 0 3 2 2                                        2   1.12                                                                             0 0 0 0 0 --                                                                              0 0 2 1 --                                                                              0 0 0 1 1                                 4      4   5.6                                                                              2 1 2 2 2 3 1 2 --                                                                              3 2 2 2 4 3 4                                        4   1.12                                                                             0 0 0 0 0 0 0 1 1 1 1 1 0 1 1 2                                 7      4   5.6                                                                              3 3 4 4 3 3 3 2 3 3 3 2 3 4 3 4                                        4   1.12                                                                             2 2 2 3 2 2 2 2 2 2 2 1 3 4 3 3                                        4   0.28                                                                             2 2 3 3 2 2 2 2 1 1 3 1 3 3 3 --                                       2   0.06                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 --                                       2   0.01                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 --                                8      4   5.6                                                                              1 0 1 2 2 2 0 2 3 1 1 0 0 2 3 3                                        2   1.12                                                                             1 0 0 0 0 0 0 1 0 0 0 0 0 0 1 2                                 __________________________________________________________________________     -- Plant species absent during test.                                     

From the test results presented in Tables I and II, it can be seen thatthe post-emergent herbicidal activity of the compounds of this inventionis, for the most part, general in nature. In certain specific instances,however, some selectivity is demonstrated. In this regard it should berecognized that each individual species selected for the above tests isa representative member of a recognized family of plant species.

The herbicidal compositions, including concentrates which requiredilution prior to application to the plants, of this invention containfrom 5 to 95 parts by weight of at least one compound of this inventionand from 5 to 95 parts by weight of an adjuvant in liquid or solid form,for example, from about 0.25 to 25 parts by weight of wetting agent,from about 0.25 to 25 parts by weight of a dispersant and from 4.5 toabout 94.5 parts by weight of inert liquid extender, e.g., water,acetone, tetrahydrofuran, all parts being by weight of the totalcomposition. Preferably, the compositions of this invention contain from5 to 75 parts by weight of at least one compound of this invention,together with the adjuvants. Where required, from about 0.1 to 2.0 partsby weight of the inert liquid extender can be replaced by a corrosioninhibitor such as ethanol mercaptan, sodium thiosulfate, dodecylmono ordimercaptan or anti-foaming agent such as a dimethylpolysiloxane, orboth. The compositions are prepared by admixing the active ingredientwith an adjuvant including diluents, extenders, carriers andconditioning agents to provide compositions in the form offinely-divided particulate solids, pellets, solutions, dispersions oremulsions. Thus, the active ingredient can be used with an adjuvant suchas a finely-divided solid, a liquid or organic origin, water, a wettingagent, a dispersing agent, an emulsifying agent or any suitablecombination of these.

The herbicidal compositions of this invention, particularly liquids andsoluble powders, preferably contain as a conditioning agent one or moresurface-active agents in amounts sufficient to render a givencomposition readily dispersible in water or in oil. The incorporation ofa surface-active agent into the compositions greatly enhances theirefficacy. By the term "surface-active agent", it is understood thatwetting agents, dispersing agents, suspending agents and emulsifyingagents are included therein. Anionic, cationic and nonionic agents canbe used with equal facility.

Preferred wetting agents are alkyl benzene and alkyl naphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long chainacid esters of sodium isothionate, esters of sodium sulfosuccinate,sulfated or sulfonated fatty acid esters petroleum sulfonates,sulfonated vegetable oils, polyoxyethylene derivatives of phenols andalkylphenols (particularly isooctylphenol and nonylphenol) andpolyoxyethylene derivatives of the mono-higher fatty acid esters ofhexitol anhydrides (e.g., sorbitan). Preferred dispersants are methylcellulose, polyvinyl alcohol, sodium lignin, sulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalene sulfonate, polymethylenebisnaphthalenesulfonate and sodium N-methyl-N-(long chain acid)taurates.

The following list gives some specific herbicidal compositions of thisinvention. It is to be realized that the solvents and surfactants areinterchangeable in the composition.

    ______________________________________                                        1.    Glycine, N--[[bis(2-furanylmethoxy)-                                                                 95 parts                                               phosphinyl]methyl]-, ethyl ester                                              Methanol               5 parts                                          2.    Glycine, N--[[bis[(2,2-dimethyl-1,3-                                                                 5 parts                                                dioxolan-4-yl)methoxy]phosphinyl]-                                            methoxy]-, ethyl ester                                                        Ethoxylated nonyl phenol                                                                             5 parts                                          3.    Glycine, N--[[bis(tetrahydro-2H--                                                                    90 parts                                               pyran-2-yl-methoxy)phosphinyl]-                                               methyl]-, ethyl ester                                                         Isopropanol            10 parts                                         4.    Glycine, N--[[bis(2-furanylmethoxy)-                                                                 90 parts                                               phosphinyl]methyl]-, ethyl ester                                              Ethoxylated octyl phenol                                                                             10 parts                                         5.    Glycine, N--[[bis[(2,2-dimethyl-1,3-                                                                 90 parts                                               dioxolan-4-yl)methoxy]phosphinyl]-                                            methoxy]-, ethyl ester                                                        Chloroform             5 parts                                                Ethoxylated dinonyl phenol                                                                           5 parts                                          6.    Glycine, N--[[bis(tetrahydro-2H--                                                                    75 parts                                               pyran-2-yl-methoxy)phosphinyl]-                                               methyl]-, ethyl ester                                                         α-butyrolactone  25 parts                                         7.    Glycine, N--[[bis(2-furanylmethoxy)-                                                                 75 parts                                               phosphinyl]methyl]-, ethyl ester                                              Ethoxylated oleyl alcohol                                                                            25 parts                                         8.    Glycine, N--[[bis[(2,2-dimethyl-1,3-                                                                 75 parts                                               dioxolan-4-yl)methoxy]phosphinyl]-                                            methoxy]-, ethyl ester                                                        Acetonitrile           15 parts                                               Ethoxylated cocoamine  10 parts                                         9.    Glycine, N--[[bis(tetrahydro-2H--                                                                    75 parts                                               pyran-2-yl-methoxy)phosphinyl]-                                               methyl]-, ethyl ester                                                         1,2-Dimethoxyethane    20 parts                                               Ethoxylated tallow amine                                                                             5 parts                                          10.   Glycine, N--[[bis(2-furanylmethoxy)-                                                                 50 parts                                               phosphinyl]methyl]-, ethyl ester                                              Dimethylformamide      50 parts                                         11.   Glycine, N--[[bis[(2,2-dimethyl-1,3-                                                                 50 parts                                               dioxolan-4-yl)methoxy]phosphinyl]-                                            methoxy]-, ethyl ester                                                        Isopropyl dodecylbenzene sulfonate                                                                   50 parts                                         12.   Glycine, N--[[bis(2-furanylmethoxy)-                                                                 50 parts                                               phosphinyl]methyl]-, ethyl ester                                              Dimethylsulfoxide      40 parts                                               Ethoxylated soybeanamine                                                                             10 parts                                         13.   Glycine, N--[[bis-[2-(1-pyrroli-                                                                     50 parts                                               dinyl)ethoxy]phosphinyl]methyl]-,                                             ethyl ester                                                                   butyrolactone          25 parts                                               Triethanolamine dodecylbenzene                                                                       25 parts                                               sulfonate                                                               14.   Glycine, N--[[bis-[2-(1-pyrroli-                                                                     50 parts                                               dinyl)ethoxy]phosphinyl]methyl]-,                                             ethyl ester                                                                   1,1,1-Trichloroethane  42 parts                                               Ethoxylated nonyl phenol                                                                             8 parts                                          15.   Glycine, N--[[bis-[2-(1-pyrroli-                                                                     25 parts                                               dinyl)ethoxy]phosphinyl]methyl]-,                                             ethyl ester                                                                   Chloroform             75 parts -16.                                                                           Glycine, N--[[bis-[2-(1-pyrroli- 25                                            parts                                       dinyl)ethoxy]phosphinyl]methyl]-,                                             ethyl ester                                                                   Chloroform             70 parts                                               Ethoxylated tallow amine                                                                             5 parts                                          17.   Glycine, N--[[bis(2-furanylmethoxy)-                                                                 25 parts                                               phosphinyl]methyl]-, ethyl ester                                              1,1,1-Trichloroethane  74 parts                                               Ethoxylated oleyl alcohol                                                                            1 part.sup.                                      18.   Glycine, N--[[bis[(2,2-dimethyl-1,3-                                                                 10 parts                                               dioxolan-4-yl)methoxy]phosphinyl]-                                            methoxy]-, ethyl ester                                                        Chloroform             90 parts                                         19.   Glycine, N--[[bis(tetrahydro-2H--                                                                    10 parts                                               pyran-2-yl-methoxy)phosphinyl]-                                               methyl]-, ethyl ester                                                         Methanol               80 parts                                               Polyoxypropylene - polyoxyethylene                                                                   10 parts                                               block copolymer                                                         20.   Glycine, N--[[bis(2-furanylmethoxy)-                                                                 10 parts                                               phosphinyl]methyl]-, ethyl ester                                              Ethanol                88 parts                                               Polyoxyethylene (20) sorbitan-                                                                       2 parts                                                monolaurate                                                             21.   Glycine, N--[[bis[(2,2-dimethyl-1,3-                                                                 10 parts                                               dioxolan-4-yl)methoxy]phosphinyl]-                                            methoxy]-, ethyl ester                                                        Isopropanol            72 parts                                               Polyoxyethylene sorbitan-                                                                            18 parts                                               monooleate                                                              22.   Glycine, N--[[bis-[2-(1-pyrroli-                                                                     5 parts                                                dinyl)ethoxy]phosphinyl]methyl]-,                                             ethyl ester                                                                   Acetonitrile           90 parts                                               Ethoxylated tallow amine                                                                             5 parts                                          23.   Glycine, N--[[bis(tetrahydro-2H--                                                                    5 parts                                                pyran-2-yl-methoxy)phosphinyl]-                                               methyl]-, ethyl ester                                                         Isopropanol            80 parts                                               Ethoxylated cocoamine  15 parts                                         ______________________________________                                    

The ingredients for examples 24-43 are blended and ground toapproximately 20-40 mesh to give the final formulation. Other wettingagents and water-soluble fillers may be employed if desired. In the listfollowing hereafter

E=Butanoic acid,3-[[[[(2-ethoxy-2-oxoethyl)amino]methyl]hydroxyphosphinyl]oxy]-, ethylester

F=Glycine, N-[[(2,2,2-trichloroethoxy)hydroxyphosphinyl]methyl]-, ethylester, hydrate

G=Glycine, N-[[hydroxy(2,2,2-trichloroethoxy)phosphinyl]methyl]-, ethylester

H=Propanoic acid,2-[[[[(2-ethoxy-2-oxoethyl)amino]methyl]hydroxyphosphinyl]oxy]-, methylester.

    ______________________________________                                         Formulation No.                                                              ______________________________________                                        Composition:                                                                              24       25     26     27   28                                    ______________________________________                                        E           80.00    90.00  95.00  98.50                                                                              100                                   Aerosol OTB 2.00     2.00   2.00   1.50 0                                     Urea        18.00    8.00   3.00   0    0                                     ______________________________________                                        Composition:                                                                              29           30     31                                            ______________________________________                                        F           80.00        90.00  95.00                                         Sodium lauryl-                                                                            2.00         2.00   1.50                                          sulfate                                                                       Urea        18.00        8.00   3.50                                          ______________________________________                                        Composition:                                                                              32     33     34   35   36   37   38                              ______________________________________                                        G           10.00  25.00  45.00                                                                              65.00                                                                              80.00                                                                              90.00                                                                              99.00                           nonyl phenol-                                                                             1.00   2.00   2.00 3.00 4.00 5.00 1.00                            poly oxyethyl-                                                                ene ether                                                                     monoammonium-                                                                             89.00  73.00  53.00                                                                              32.00                                                                              --   --   --                              phosphate                                                                     sucrose     --     --     --   --   16.00                                                                              5.00 --                              ______________________________________                                        Composition:                                                                              39      40     41     42   43                                     ______________________________________                                        H           80.00   90.00  95.00  98.50                                                                              100                                    Aerosol OTB 2.00    2.00   2.00   1.50 0                                      Urea        18.00   8.00   3.00   0    0                                      ______________________________________                                    

When operating in accordance with the present invention, effectiveamounts of the compounds or compositions of this invention are appliedto the plants, or to soil containing the plants, or are incorporatedinto aquatic media in any convenient fashion. The application of liquidand particulate solid compositions to plants or soil can be carried outby conventional methods, e.g., power dusters, boom and hand sprayers andspray dusters. The compositions can also be applied from airplanes as adust or a spray because of their effectiveness at low dosages. Theapplication of herbicidal compositions to aquatic plants is usuallycarried out by adding the compositions to the aquatic media in the areawhere control of the aquatic plants is desired.

The application of an effective amount of the compounds or compositionsof this invention to the plant is essential and critical for thepractice of the present invention. The exact amount of active ingredientto be employed is dependent upon the response desired in the plant aswell as such other factors as the plant species and stage of developmentthereof, and the amount of rainfall as well as the specific glycineemployed. In foliar treatment for the control of vegetative growth, theactive ingredients are applied in amounts from about 0.112 to about 56.0or more kilograms per hectare. In pre-emergent treatments, the rate ofapplication can be from about 0.56 to about 22.4 or more kilograms perhectare. In applications for the control of aquatic plants, the activeingredients are applied in amounts of from about 0.01 parts per millionto about 1000 parts per million, based on the aquatic medium. Aneffective amount for phytotoxic or herbicidal control is that amountnecessary for overall or selective control, i.e., a phytotoxic orherbicidal amount. It is believed that one skilled in the art canreadily determine from the teachings of this specification, includingexamples, the approximate application rate.

There are several methods for applying liquid compositions of thisinvention to emerged plants. Such methods include the use of wipersystems whereby the plant to be treated is contacted with an absorbentmaterial containing the particular liquid composition, a portion ofwhich is thereby released onto the plant upon contact therewith. Suchwiper systems typically comprise a reservoir of the liquid compositioninto which a portion of the absorbent material is placed and is fedtherethrough. Generally, substances employable as absorbent materialinclude substances of any shape or form capable of absorbing the liquidcomposition and releasing a portion of the same upon contact with theplant. Typical absorbent materials include felt, foam rubber, cellulose,nylon, sponges, hemp, cotton, burlap, polyester over acrylic,combinations thereof and the like. Forms of absorbent material includerope, twine, string, cloths, carpets, combinations thereof and the like.These forms may be assembled in any manner desired including a pipe ropewick, a wedge rock wick, a multi-rope wick and the like.

In another application method, liquid compositions may be selectivelyapplied to weeds by the use of recirculating sprayer systems wherein therecirculating spray unit is mounted on a tractor or high clearancemobile equipment and the spray is directed horizontally onto the weedsgrowing over a crop. Spray not intercepted by the weeds is collected ina recovery chamber before contacting the crop and is reused. Rollerapplications may also be employed to apply liquid compositions to weedsgrowing over a crop.

In yet another application method, shielded applicators may be employedto direct the liquid composition in the form of a spray onto the weedswhile effectively shielding the crops from the spray.

These and other application methods for selectively applying liquidcompositions to weeds are discussed in detail in Innovative Methods ofPost-Emergence Weed Contol, McWhorter C. G, Southern Weed ScienceSociety, 33rd Annual Meeting Proceedings, Jan. 15-17, 1980; AuburnUniversity Printing Service, Auburn, Ala. U.S.A., the teachings of whichare incorporated herein by reference in their entirety.

Another method of applying liquid compositions of this invention toplants includes controlled droplet application which is also known asthe ultra low-volume chemical application. Controlled dropletapplication involves the production of uniform or nearly uniform spraydrops of a predetermined size and the conveyance of these drops withnegligible evaporation to a spray target. In particular, this methodcomprises feeding spray solutions to a rotary atomizer comprising asmall disk with serrated edges that disperses liquid into droplets asthe disk spins. Different droplet sizes are produced by changingsolution flow rates to the spinning disk or changing the speed ofrotation of the disk.

The aforementioned and other methods for applying liquid compositions toplants are discussed in detail in "Rope Wick Applicator--Tool With AFuture", Dale, James E., pp. 3-4, "The Recirculating Sprayer andRoundup® Herbicide", Derting, Claude W., pp. 5-7, and "C.D.A. HerbicideApplication", McGarvey, Frank X., Weeds Today, Volume 11, Number 2, pp.8-9, Late Spring, 1980, 309 W. Clark St., Champaign, Ill., the teachingsof which are incorporated herein by reference in their entirety.

Although this invention has been described with respect to specificmodifications, the details thereof are not to be construed aslimitations, for it will be apparent that various equivalents, changesand modifications may be resorted to without departing from the spiritand scope thereof and it is understood that such equivalent embodimentsare intended to be included herein.

What is claimed is:
 1. Alkylphosphonate esters ofN-phosphonomethylglycinate of the formula ##STR9## wherein R is loweralkyl; R₁ is a ##STR10## group wherein n is an integer of from 0 to 4, Lis hydrogen or lower alkyl and Y is selected from the group consistingof trihalomethyl, alkoxycarbonyl, furanyl, pyrrolidinyl, pyranyl groupand a ##STR11## group wherein Z and Z₁ are independently lower alkyl,and R₂ is hydrogen or a group represented by R₁ provided that when Y isalkoxycarbonyl, R₂ is hydrogen.
 2. A compound of claim 1 wherein R isethyl.
 3. A compound of claim 1, wherein R₂ is the same group asrepresented by R₁ and R is ethyl.
 4. A compound of claim 1 wherein R₁ is--(C_(n) H_(2n))--Y n is an integer from 1 to 4, and R is ethyl.
 5. Acompound of claim 4 wherein Y is furanyl.
 6. A compound of claim 4wherein Y is dioxolanyl.
 7. A compound of claim 4 wherein Y is pyranyl.8. A compound of claim 3, wherein R₁ is --(C₂ H₄)--Y, wherein Y ispyrrolidinyl.
 9. A compound of claim 2, wherein R₂ is hydrogen.
 10. Acompound of claim 9, wherein R₁ is --(C_(n) H_(2n))--Y.
 11. A compoundof claim 10, wherein n is
 2. 12. A compound of claim 11, wherein Y isethoxycarbonyl.
 13. A compound of claim 11, wherein Y istrichloromethyl.
 14. A compound of claim 10, wherein n is 1 and Y istrichloromethyl.
 15. A compound of claim 10, wherein n is 4 and Y isethoxycarbonyl.
 16. A herbicidal composition comprising a herbicidallyeffective amount of a compound of claim 1, together with an inertdiluent.
 17. A herbicidal composition comprising a herbicidallyeffective amount of a compound of claim 2, together with an inertdiluent.
 18. A herbicidal composition comprising a herbicidallyeffective amount of a compound of claim 3, together with an inertdiluent.
 19. A herbicidal composition comprising a herbicidallyeffective amount of a compound of claim 4, together with an inertdiluent.
 20. A herbicidal composition comprising a herbicidallyeffective amount of a compound of claim 5, together with an inertdiluent.
 21. A herbicidal method which comprises contacting a plant witha herbicidally effective amount of a compound of claim
 1. 22. Aherbicidal method which comprises contacting a plant with a herbicidallyeffective amount of a compound of claim
 2. 23. A herbicidal method whichcomprises contacting a plant with a herbicidally effective amount of acompound of claim
 3. 24. A herbicidal method which comprises contactinga plant with a herbicidally effective amount of a compound of claim 4.25. A herbicidal method which comprises contacting a plant with aherbicidally effective amount of a compound of claim 5.